CN1088743C - Colorless petroleum markers - Google Patents

Colorless petroleum markers Download PDF

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Publication number
CN1088743C
CN1088743C CN96194717A CN96194717A CN1088743C CN 1088743 C CN1088743 C CN 1088743C CN 96194717 A CN96194717 A CN 96194717A CN 96194717 A CN96194717 A CN 96194717A CN 1088743 C CN1088743 C CN 1088743C
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marker
petroleum products
solution
solvent
alkyl
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CN1187844A (en
Inventor
迈克尔·J·史密斯
巴拉特·德赛
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United Color Manufacturing Inc
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United Color Manufacturing Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/20—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/007—Coloured or dyes-containing lubricant compositions

Abstract

A marker for petroleum products which can be detected upon addition of a developing reagent which develops color when is contact with the marker.

Description

Colourless petroleum markers
Background of invention
The present invention relates to colourlessly or subdiaphanous be used for mark or indicate oil-fired compound.The present invention also relates to be used for the colouring reagents of the marker that alkali can extract.The invention still further relates to the method for the color of the marker that bleaching developed the color, thereby make fuel recover original appearance and can mix mutually, avoided the needs of the common proemial marker extraction liquid of independent disposal in the prior art with the fuel that is labeled without colour developing.
Marker is to be used to indicate that petroleum products for the material that detects subsequently, is colourless in petroleum products usually.Marker is dissolved in to be waited to know in other fluids, and then fluid is made simple physics or test chemical detects to being labeled.Sometimes government needs marker to guarantee that specific rank fuel has been imposed suitable tax revenue.The oil company also marks to help identification to dilute or change the people of its product to its product.These companies often do very big cost and meet some specification to guarantee its famous brand petroleum products, as volatility and octane value, also will provide enough additive packings that comprises washing composition and other components for its petroleum products simultaneously.The human consumer then trusts brand and guarantees that product purchases the quality mark of selling by desired quality.
Concerning the gasoline merchant that those are not paid attention to morals, peddling the product of inferior quality with the price that can be used to buy high-quality famous brand or appointed product to the human consumer can increase profit.Also the wearing or featuring stage armour best brand of product improves profit with the way that the product of inferior quality dilutes simply.It is difficult will rectifying the businessman that replaces a certain product or mix the product of inferior quality in best brand of product with another kind of product concerning gasoline products, because also show each composition of best brand of product in the qualitative reaction of mixing prod.And the common content of crucial additive in the best brand of product is very low, and the quantitative analysis that detects the degree of being diluted by the product of inferior quality like this will be difficult, the time-consuming costliness that reaches.
The label method of system of fuel or other petroleum productss is suggested, but because various shortcoming has hindered its usefulness.A lot of Mk systems as losing efficacy in time, make to be difficult to test through after the Long-term Storage.In addition, be used to make the reagent of marker colour developing usually to be difficult to operation or to have handling problems.And some marker also can be assigned in the water.When in aqueous container, storing, can cause marker to lose efficacy.
Contain the compound that often is described to the hydroxyl phthaleins in the present composition.Be established as range estimation pH indicator in the acid of some compounds wherein/alkalimetric titration analysis in the laboratory.Also have some recommended being applicable in some biopharmaceutical application.But they are marked in oil fuel and additive or the purposes of mark still is unique.
The similar compound that has been considered as marker is a phenolphthalein.It was recommended as the fuel marker by U.S.Environmental Protection Agency in 1994, and carried out the experiment in petroleum refining field under it is sponsored.Because phenolphthalein lacks suitable solubleness in oil fuel under the desired concentration of mark, experiment is not succeeded.Phenolphthalein partial crystallization from fuel is separated out, and causes the bottom of refining unit, pipeline etc. to be labeled and pollutes.Phenolphthalein is also soluble in water, and the water layer that usually combines in storage tank bottom can be with its part extraction, therefore causes it can not be as quantitative fuel marker.In addition, phenolphthalein is responsive especially to the alkalescence of extraction liquid or developer.With pH during less than 10.5 water base extraction liquid, extraction is slow and not exclusively, and pH is higher than the about 11 o'clock colourless trianions of the very fast formation of phenolphthalein.Material of the present invention does not have these shortcomings.
Marker of the present invention has bigger solubleness and littler solubleness is arranged in neutral water in oil fuel.Two anionic parts were faded and also are minimized under susceptibility that its trianion forms and highly basic existed.The appearance of these advantages have benefited from marker of the present invention in adjacent alkyl or the alkoxyl group of ionizable hydroxyl.
Marker of the present invention is colourless in aqueous petroleum products when effective usage quantity, but when extracting with suitable developer expression characteristics color then.The reagent that is used to develop the color itself also is easy to use, operate and dispose.
Mark of the present invention does not make the feature of oil fuel band look make it be widely used in petroleum products under the effective level level.As can be used for the low-sulfur diesel-oil that mark or sign are used for road vehicle at present.Stop in the regulations of federal government's promulgation and in this fuel, add the dyestuff or the relevant material of dyestuff that can make the fuel tape look by effective level.These regulations have been got rid of the use of recommending in the prior art as the multiple strong band color substance of oil fuel marker, as, United States Patent (USP) 5,156,653; 5,205,840; Disclosed material in 4,764,474 and 4,735,631.The content of these patents is hereby incorporated by.
The invention summary
But the present invention includes the marker composition and comprise aqueous petroleum products and the composition of the marker of detection limit, wherein marker is 1 (3H) derivatives of isobenzofaranone:
Figure C9619471700121
R wherein 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group.R 4Bromine, chlorine and hydrogen atom for arbitrary combination.
In addition, R 2And R 3The naphthalene nucleus components of system as directed of carbon atom shown in can being constructed as follows:
Figure C9619471700131
R wherein 1-R 4As mentioned above, R 5For hydrogen atom, contain the alkyl or the alkoxyl group of 1 to 8 carbon atom.
The present invention also comprises a kind of method of tagged petroleum products, but comprises the marker that adds detection limit in aqueous petroleum products, and this marker is selected from:
Figure C9619471700132
Figure C9619471700141
R wherein 1-R 5As mentioned above.
The present invention also is a kind of method of identifying aqueous petroleum products, but in the method to the above-mentioned aqueous petroleum products sampling that contains the marker of detection limit, adds chromogenic reagent then in sample.
The present invention also comprises a kind of method of identifying aqueous petroleum products, but in the method to the petroleum products sampling of the thymolphthalein marker that contains detection limit, adds developer then and marker is extracted in the spe medium in sample.
The present invention also comprises a kind of solution of tagged petroleum products, and it comprises above-mentioned marker and marker solvent that can be miscible with petroleum products.Detailed Description Of The Invention
Marker of the present invention can be added into any petroleum products such as fuel, lubricating oil and lubricating grease.The example of the aqueous petroleum products of the present invention has gasoline, diesel oil, oil fuel, kerosene and lam-oil.Back visualize in wide concentration range but mark is developed the color, but preferred content is at least about 0.5ppm to 5ppm, and more preferably about 0.5 to about 100ppm.
Because marker is colourless basically in petroleum products, be with photographic developer or developer and its existence of its reaction detection.The developer of Shi Yonging must contain highly basic such as alkali-metal oxyhydroxide in the present invention, or most preferred quaternary ammonium hydroxide.The pH value of developer is about 10 to about 14, is preferably about 11 to about 13.In case contact developer ionization and rapid two negatively charged ion that form the strong band look with the alkali of being recommended.The intensity of the marker of colour developing is easy to visual detection.If only need qualitative indication is done in the existence of developer, the fuel of band look, " colour developing " can be backed its source.Developer and marker are burnt with product or are used up like this, do not cause the accumulation of the proemial waste that will dispose in as the roadside experiment.Before in the sample that contains the marker of colour developing being backed its initial source, add with the mixable acid of fuel the color of the commodity that develop the color is destroyed, be preferably organic carboxyl acid such as oleic acid or Unimac 5680.Contain " colour developing " fuel active, unreacted developer though added like this, the fuel in the source is not also by color stain.
When the color of marker of colour developing by petroleum products in other staining agent when covering, with the spe medium extraction fuel that developed the color, the marker that developed the color is manifested.Can only use water as spe medium and finish extraction, but the mixture of preferred water and phase separation promoter such as Fatty Alcohol(C12-C14 and C12-C18), ethylene glycol or glycol ether is as spe medium sample.The use promotion water and the organic phase of phase separation promoter are more easily separated.In addition, other materials also can be present in the extraction phase to stablize two negatively charged ion or marker as the pH buffering salt.Preferred spe medium mixture also comprises the quaternary phosphonium hydroxides ammonium compound, so that the suitable medium that can be extracted immediately by the marker that forms simple method that two negatively charged ion or marker develop the color and colour developing to be provided.Certainly, other highly basic, particularly alkali-metal oxyhydroxide also can use.
Be the existence of qualitative definite marker, can do visual examination extraction phase.In addition, the also available visible absorption spectrophotometry of the marker that is extracted detects and is quantitative.The benefit of extracting operation is the marker in the energy enrichment oil fuel, thereby has increased the sensitivity of detection method.
Marker of the present invention is represented with following structural: R wherein 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group.R 4Bromine, chlorine or hydrogen atom for arbitrary combination.R 1, R 2And R 3Middle alkyl carbon sum preferably is no more than 12.
In addition, R 2And R 3The naphthalene nucleus components of system as directed of carbon atom shown in can being constructed as follows:
Figure C9619471700162
R wherein 5For hydrogen atom, contain the alkyl or the alkoxyl group of 1 to 8 carbon atom.
Compound of the present invention can be synthetic with any means in the multiple common method, relate to 1 of a molar equivalent in the synthetic method, the 2-phthalic acid, or preferred Tetra hydro Phthalic anhydride and the 2-alkylphenol of two molar equivalents or the condensation of 1-naphthols, wherein with respect to 4 carbon atoms of 1 aromatic ring hydroxyl to reacting useful.Actual condensation reaction need add thermal initiation, preferably in the presence of dehydracetic acid such as ortho-phosphoric acid, sulfuric acid or methylsulfonic acid, or is used in and be the metal halide of reactive behavior, particularly aluminum chloride, tin chloride or zinc chloride initiation in the Friedel-Crafts reaction.When the United States Patent (USP) 2,522,939 and 2,522 of pressing the synthetic phenolphthalein of Gamrath, when 940 synthetic methods of being recommended were synthesized, the catalyzer that above-mentioned back proposes was effective especially.Whole patent disclosures of quoting two patents herein as a reference.Dehydracetic acid and Friedel-Crafts metal halide associating result of use are also satisfactory.
Tagged compound can powder or form or the aqueous concentrated solution form done such as crystal use.Because of the reason of operating is preferably aqueous form usually.
For the strong solution that contains marker is provided, marker is dissolved in or to solvent, is formed in the non-aqueous solution that high-dissolvability is arranged in the petroleum products towards rare.The solvent that petroleum products is suitable for comprises, as aromatic hydrocarbons, alkylbenzene particularly is as dimethylbenzene and naphthalene compounds; Fragrant and mellow, particularly benzylalcohol and phenol glycol ether; With aprotic solvent such as methane amide, N, dinethylformamide, N,N-dimethylacetamide or 1-methyl-2-pyrrolidone.These solvents can use separately or mix use for the purpose of favourable.After appropriate solvent of the present invention and marker mixing, constituted the stable liquid composition that is soluble in petroleum products.Mainly be because fluid is more easy to operate, so, with do or solid phase prod compare, use marker stable, free-pouring fluid form that petroleum industry is had more magnetism.Certainly also can directly use dried or solid marker.
For example by weight, common aqueous strong solution can comprise the marker of about 5-50wt% and the solvent of about 50-95wt%.The preferable range of solution can be the marker of 15-25wt% and the solvent of 75-85wt%.As mentioned above, the solvent of Shi Yonging comprises aprotic solvent and aromatic solvent.The consumption of the aprotic solvent that comprises in the solution depends on relative price and other factors known in the art of the addition of marker, the viscosity of solution, the aprotic solvent that adopts.Being used for the aromatic solvent of a certain specific aqueous strong solution or the selection of cosolvent decides according to the type of petroleum products to be marked.For example, easy volatile solvent is used for the mark gasoline products, and easy volatile solvent then is not used in the aqueous strong solution that is used for mark and identifies diesel oil or family expenses heated oil product.
A special shape of the marker that adopt in this place is a thymolphthalein.Its structure is represented with following formula:
Figure C9619471700181
It can generate by the phthalic acid of a molar equivalent or 2-sec.-propyl-5-methylphenol (thymol) condensation in the presence of dehydrating agent such as phosphoric acid, tin chloride or zinc chloride of Tetra hydro Phthalic anhydride and two molar equivalents.Recommend synthetic this compound of synthesis methods can good yield by the disclosed phenolphthalein of U.S. Patent No. 2,522,939, clearly introduce its whole patent disclosure herein as a reference.
Form that thymolphthalein can be done (powder commonly used or crystal) or liquid strong solution form are used.Strong solution can by marker with can with the solvent preparation of petroleum products complete miscibility to be marked.Because directly dissolved solubleness is more limited in the straight chain petroleum hydrocarbon for thymolphthalein, it is particularly advantageous comprising aprotic solvent in the solvent compositions, 1-Methyl-2-Pyrrolidone particularly, and it can increase the solubleness of thymolphthalein in hydrocarbon greatly.Other and the useful solvent of thymolphthalein blended comprise suitable aromatic hydrocarbon, particularly alkylbenzene, as dimethylbenzene, and naphthalene compounds; Aromatic alcohols, particularly benzylalcohol and phenol glycol ether; With other aprotic solvent, particularly methane amide, N, dinethylformamide and N,N-dimethylacetamide.For example, by weight, the composition that comprises thymolphthalein can comprise the marker of about 5-50wt%, the aprotic solvent of about 5-50wt% and the aromatic solvent of about 0-90wt%.Adopt the thymolphthalein thing of marking, and the aqueous strong solution particularly suitable that comprises the aromatic solvent of the aprotic solvent of the marker of about 10-30wt%, about 10-40wt% and about 30-80wt% is soluble in also stable composition therein of most of petroleum productss; Be that said composition keeps dissolved state in the commodity validity period in petroleum products.
When particularly mixing mutually with appropriate solvent, thymolphthalein of the present invention and other compounds have constituted and have been soluble in liquid composition petroleum products, stable.Mainly be because fluid is more easy to operate, thus with do or solid phase prod compare, use marker stable, free-pouring fluid form that petroleum industry is had more magnetism.Certainly also can directly use dried or solid marker.
The following example only is used to describe the present invention, and does not have the demarcation effect.
Embodiment 1
In one liter of glass flask that a band stirs, add the anhydrous methylsulfonic acid of 400 grams.Add 200 gram 2-sec.-propyl-5-methylphenols (thymol), and then add 110 gram Tetra hydro Phthalic anhydrides.Reaction mixture is heated to 85 ℃, and keeps 5 hours under this temperature.When product takes on a red color the granular solids precipitation with its father-in-law's salt form, flask contents is poured in 1500 milliliters of well-beaten cold water.In stirred mixture, add 40% sodium hydroxide solution of capacity, make the pH value rise to 4.Make father-in-law's salt hydrolysis, product changes light orange look solid into.Product is told in filtration, with cold wash and dry down in 70 ℃.Make 256 gram products, wherein contain active thymolphthalein 76.7%.Productive rate is 68.5%.
Embodiment 2
Repeat above-mentioned synthetic operation, difference is that Tetra hydro Phthalic anhydride changes 40 gram Aluminum chloride anhydrouss into.Reaction mixture is heated to 85-90 ℃, and keeps 4 hours, has a large amount of spirit of salt gases to emit therebetween.Then reaction mixture being poured in the cold water and is neutralized to pH with sodium hydroxide is 2.Precipitated product is told in filtration, and washing is also dry.Make 235 gram products, its color is more of light color than product among the embodiment 1.Contain active thymolphthalein 84.2%, be equivalent to 74.9% of theoretical yield approximately.
Embodiment 3
In one liter of flask that a band stirs, add the anhydrous methylsulfonic acid of 500 grams, 110 gram Tetra hydro Phthalic anhydrides and 144 gram ortho-cresols.Mixture heating up to 40 ℃ then adds 40 gram Aluminum chloride anhydrouss.Mixture heating up to 85 ℃ also kept 4 hours.Then be poured in the cold water also with aqueous sodium hydroxide solution adjust pH to 2.Precipitated product is told in filtration, and washing is also dry.Make 160 gram canescence products, wherein contain cresolphthalein 98.2%.Be equivalent to 68.1% of theoretical yield.
Embodiment 4
Repeat the operation of embodiment 3, difference is, 144 gram ortho-cresols are changed into 235 gram 2-cyclohexylphenol.Make 215.8 gram Off-white solid, wherein contain actives 79.5%, be 65% of theoretical yield.Embodiment 5
Repeat the operation of embodiment 1, difference is, 200 gram 2-sec.-propyl-5-methylphenols are changed into 195 gram 1-naphthols (purity 98%).Make 255 gram crude products.
Embodiment 6
20 gram thymolphthaleins are joined 50 restrain in the mixed methylnaphthalene solvent of selling with trade(brand)name Exxon Aromatic 200 under stirring, then add 30 gram 1-methyl-2-pyrrolidones.Mixture heating up to 40 ℃ is until all ester matter dissolvings, and hot solution is filtered and bottles.Do not have crystallization at 0 this solution of following long storage and separate out tendency.
Embodiment 7
Warm following 50 gram thymolphthalein is dissolved in the 50 gram 1-methyl-2-pyrrolidones.Filter back solution good storage stability is arranged under 0 °F.
Embodiment 8
The solution that 500 milligrams of embodiment 1 are made is dissolved in the toluene, and is diluted to 100ml in marked flask.This drips of solution of 1.0ml is added to 100ml has used the Unisol LiquidRed B (brand that United Color Mfg. adopts, main color-producing bodies is C.I.Solvent Red 164 in the dyestuff) of 3ppm to dye premium motor fuel (retail is buied) red, that place separating funnel.Contain the thymolphthalein that the is equivalent to 10ppm thing that serves as a mark in the gasoline sample.5ml is contained the aqueous solution that 15% sodium-chlor and being enough to makes the pH value rise to 12 sodium hydroxide be added to the gasoline that is labeled that places separating funnel.Two-phase is then let alone layering by jolting together two to three minutes.Upper strata gasoline still keeps light red mutually, and lower floor's water then is mazarine.Can come out aqueous phase separation and with spectrophotometry blue dyes is done quantitative analysis in about 590 nanometers of maximum absorption.
Embodiment 9
Except that thymolphthalein changes in toluene solution to the 20ppm, with distilled, be close to wasserhelle gasoline and repeat to implement 8 operation.The existence of marker does not change the visual appearance of gasoline.
Embodiment 10
5ml is blended in the gasoline that 95ml is not labeled by the coloured gasoline that is labeled of embodiment 8 preparation, then extracts this mixture with alkali salt water by the operation among the embodiment 8.Even mutually the blueness that can arouse attention is arranged also at low like this marker concentrations horizontal launching, if desired, make comparisons with the standard correction curve and also can do quantitative instrumental analysis dyestuff.
Embodiment 11
In 50 milliliters of gasoline that incarnadined that contain the 10ppm thymolphthalein, add 5 milliliters of 10% tetrabutylammonium ethylene glycol propyl ether solution as reagent composition.Show the feature blueness after the mixture jolting several seconds kind, under the gasoline red background, can clearly see.If only need make qualitative detection, the gasoline that is labeled that has developed the color can be backed in its fuel source; This has been avoided the problem of independent being potentially dangerous property of disposal waste.If desired or the expectation marker is made detection by quantitative, the background interference that depends on other components in the fuel can directly detect with spectrophotometry.In addition, also 10% sodium-chlor distilled water solution of 5ml equal portions can be added in the fuel that is labeled that has developed the color.After mixture was by the short period of time jolting, blue marker two negatively charged ion were extracted into lower floor's aqueous phase, with its separation and to press embodiment 8 quantitative.Embodiment 12
In 100 milliliters of gasoline solution that contain the 15ppm thymolphthalein, add 1 milliliter of 10% hydroxide tetra-n-butyl ammonium ethylene glycol mono-n-butyl ether solution.It is blue that mixture becomes immediately, and indication has the existence of thymolphthalein marker.Then adding 1 milliliter of Unimac 5680 makes the blueness disappearance of thymolphthalein marker and makes gasoline recover original appearance.Sample can be backed in its initial source.
Embodiment 13
50 milliliters of U.S. Patent application No.08/375 that contain thymolphthalein and application on January 20 nineteen ninety-five, the diesel oil of each 5ppm of fluorescein di-n-butyl that describes in 310 (the introducing this patent disclosure herein as a reference) places 100ml clear-glass bottle, and is added to 1 milliliter of 10% hydroxide tetra-n-butyl ammonium ethylene glycol mono-n-butyl ether solution.The very fast colour developing of mixture is fluorescent blue and is fluorescence green under transmitted light under reflected light, have very significantly different with the fuel of un-marked.Can put into part solution in the cuvette, its fluorescein and thymolphthalein two anionic relative contents can 490 and 600 nanometers its separately the maximum absorption wave strong point measure.Also can make spectrophotometry in addition by the salt solution extraction phase of 8 pairs of markers of embodiment.If do not carry out this option, with marker two anionic aliquot acid, make it recover original appearance basically in then in the fuel that is labeled that has developed the color, adding.Then it can be refunded to its initial source.
Embodiment 14-21
Similar synthetic method among employing and the embodiment 1 to 5 and the coloration method among the embodiment 8, preparation are also estimated following compounds.Embodiment acid anhydrides phenol visible color absorbs the bright-coloured purple 571.5nm15 Tetra hydro Phthalic anhydride 2 of predominant wavelength 14 Tetra hydro Phthalic anhydride 2-secondary butylphenols, the reddish blue 592.5nm16 Tetra hydro Phthalic anhydride 2 that the 6-diisopropyl phenol is bright-coloured, the blue 5,97n,m19 2 of the mazarine 593.5nm17 Tetra hydro Phthalic anhydride 2-tertiary butyl that 6-two secondary butylphenols are bright-coloured-5-methylphenol reddish blue 597nm18 Tetra hydro Phthalic anhydride 2-n-butoxy phenolsulfonphthalein, 3,4,5-tetrachloro 2-sec.-propyl-5-methylphenol pure blue 621.5nm
The blue 6,55n,m21 2,3,4 of Tetra hydro Phthalic anhydride 20 Tetra hydro Phthalic anhydride 1-naphthol greens, the 5-tetrachloro
The white blue 658.5nm of Tetra hydro Phthalic anhydride 1-naphthols it should be noted the influence owing to solvation displacement effect, and above-mentioned absorption predominant wavelength may some variation under different observation conditions.
Applicant's invention is with reference to being described with the preferred embodiment.Under the condition of the scope of the invention, multiple improvement project can arranged to foregoing invention.

Claims (33)

  1. But 1, a kind of composition that comprises the marker of petroleum products and detection limit, wherein, described marker is selected from: Wherein, R 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group; R 4Be hydrogen, chlorine or bromine; R 5For hydrogen atom or contain the alkyl or the alkoxyl group of 1 to 8 carbon atom; And
    Described marker dissolves or is diluted in and forms non-aqueous solution in the solvent, and this solution is dissolved in the described petroleum products, and described marker develops the color when contacting with developer.
  2. 2, composition as claimed in claim 1, wherein, the content of described marker in described petroleum products is at least 0.5ppm.
  3. 3, composition as claimed in claim 1, wherein, the content of described marker is at least 5ppm.
  4. 4, composition as claimed in claim 1, wherein, the concentration of described marker is 0.5-100ppm.
  5. 5, composition as claimed in claim 4, wherein, described marker is:
  6. 6, composition as claimed in claim 1, wherein, R 1, R 2And R 3In total alkyl carbon number be no more than 12.
  7. 7, a kind of method of tagged petroleum products, but it comprises the marker that adds detection limit in described petroleum products, and this marker is selected from: Wherein, R 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group; R 4Be hydrogen, chlorine or bromine; R 5For hydrogen atom or contain the alkyl or the alkoxyl group of 1 to 8 carbon atom; And
    Described marker dissolves or is diluted in and forms non-aqueous solution in the solvent, and this solution is dissolved in the described petroleum products, and described marker develops the color when contacting with developer.
  8. 8, method as claimed in claim 7, wherein, the content of described marker is at least 0.5ppm.
  9. 9, method as claimed in claim 8, wherein, the content of described marker is at least 5ppm.
  10. 10, composition as claimed in claim 9, wherein, the content of described marker is 0.5-100ppm.
  11. 11, composition as claimed in claim 10, wherein, described marker adds in the described petroleum products with fluid form.
  12. 12, a kind of evaluation comprises the method for the petroleum products of marker, and it comprises:
    A) but to comprising the petroleum products sampling of detection limit marker, wherein said marker is selected from: Wherein, R 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group; R 4Be hydrogen, chlorine or bromine; R 5For hydrogen atom or contain the alkyl or the alkoxyl group of 1 to 8 carbon atom; And
    Described marker dissolves or is diluted in and forms non-aqueous solution in the solvent, and this solution is dissolved in the described petroleum products, and described marker develops the color when contacting with developer; Then
    B) add developer in above-mentioned sample, this developer develops the color when contacting with described marker.
  13. 13, method as claimed in claim 12 wherein, generates coloured two negatively charged ion with colour developing by basic hydrolysis.
  14. 14, method as claimed in claim 13, wherein, described developer comprises highly basic.
  15. 15, method as claimed in claim 14, wherein, the pH value of described developer is 10 to 14.
  16. 16, method as claimed in claim 15, wherein, described alkali is selected from alkali metal hydroxide.
  17. 17, method as claimed in claim 16, wherein, described alkali is quaternary ammonium hydroxide.
  18. 18, method as claimed in claim 17, wherein, the pH value of described reagent is 11 to 13.
  19. 19, method as claimed in claim 18 wherein, is added spe medium in described sample.
  20. 20, method as claimed in claim 19, wherein, spe medium mixes by 1 to 17 volume ratio with aqueous petroleum products.
  21. 21, method as claimed in claim 20, wherein, described spe medium is the mixture that comprises water and be selected from the phase separation promoter of Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohols, ethylene glycol and glycol ether.
  22. 22, method as claimed in claim 21, wherein, described mixture also comprises the quaternary phosphonium hydroxides ammonium compound.
  23. 23, method as claimed in claim 22, wherein, the colour developing commodity of band look add the acid neutralization, make the fuel that is labeled recover original appearance.
  24. 24, a kind of method of identifying petroleum products, it comprises:
    A) but to including the petroleum products sampling of detection limit thymolphthalein marker, described marker dissolves or is diluted in and forms non-aqueous solution in the solvent, and this solution is dissolved in the described petroleum products,
    B) in described marker, add developer, and
    C) described marker is extracted in the spe medium.
  25. 25, a kind of solution of tagged petroleum products, it comprises:
    A) a kind of marker, it is selected from:
    Figure C9619471700071
    Wherein, R 1For containing the alkyl or the alkoxyl group of 1 to 8 carbon atom; R 2And R 3Be hydrogen atom, alkyl or alkoxyl group; R 4Be hydrogen, chlorine or bromine; R 5For hydrogen atom or contain the alkyl or the alkoxyl group of 1 to 8 carbon atom; And
    Described marker develops the color when contacting with developer; And
    B) can be in described petroleum products the solvent of miscible described marker.
  26. 26, solution as claimed in claim 25, wherein, visual can not detection when described marker is in the described petroleum products.
  27. 27, solution as claimed in claim 26, wherein, described solvent is selected from aromatic hydrocarbon, aromatic alcohols and non-protonic solvent.
  28. 28, solution as claimed in claim 27, wherein, in weight ratio, described composition comprises the marker of 5-50% and the solvent of 50-95%.
  29. 29, solution as claimed in claim 28, wherein, in weight ratio, described composition comprises the marker of 15-25% and the solvent of 75-85%.
  30. 30, solution as claimed in claim 29, wherein, in weight ratio, described composition comprises the marker of 5-50%, the aromatic alcohols of 0-90% and the non-protonic solvent of 5-50%.
  31. 31, solution as claimed in claim 30, wherein, in weight ratio, described composition comprises the marker of 10-30%, the aromatic solvent of 30-80% and the non-protonic solvent of 10-40%.
  32. 32, solution as claimed in claim 31, wherein, described non-protonic solvent is selected from 1-methyl-2-pyrrolidone, N, dinethylformamide and N,N-dimethylacetamide.
  33. 33, solution as claimed in claim 32, wherein, in weight ratio, described composition comprises 20% thymolphthalein, 50% aromatic solvent and 30% 1-methyl-2-pyrrolidone.
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